US4482428A - Smooth-look footwear process - Google Patents
Smooth-look footwear process Download PDFInfo
- Publication number
- US4482428A US4482428A US06/603,057 US60305784A US4482428A US 4482428 A US4482428 A US 4482428A US 60305784 A US60305784 A US 60305784A US 4482428 A US4482428 A US 4482428A
- Authority
- US
- United States
- Prior art keywords
- etching solution
- molded
- block copolymer
- composition
- smooth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000005530 etching Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 229920001400 block copolymer Polymers 0.000 claims abstract description 15
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229920001971 elastomer Polymers 0.000 claims abstract description 7
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005060 rubber Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 229940117975 chromium trioxide Drugs 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims 1
- 239000000243 solution Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- -1 poly(vinyl chloride) Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940032007 methylethyl ketone Drugs 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2021/00—Use of unspecified rubbers as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/48—Wearing apparel
- B29L2031/50—Footwear, e.g. shoes or parts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
Definitions
- block copolymers and their compounds are being used in large volume in the manufacture of a wide variety of shoes including canvas shoes, sport shoes, and dress shoes.
- the block copolymers may be utilized for this purpose for soling, foxing, innersoles and the like.
- These compositions are disclosed in Hendricks et al, U.S. Pat. No. Re. 28,236.
- these shoe component compositions usually comprise a mixture of block copolymer, extending oil, polystyrene and possibly a filler.
- block copolymer compositions have proven to be particularly advantageous in many respects, including flexibility, processability, lack of vulcanization requirement and wet slip.
- shortcomings have been noted.
- commercial compounds should be free from delamination, free from elephant hide, and free from flow markings and marring.
- one of the major shortcomings of the block copolymer compounds such as those referred to in U.S. Pat. No. Re. 28,236 is the lack of a smooth appearance.
- Present block copolymer compounds lack the smooth, relatively unblemished surface which is characteristic of compression molded vulcanized conventional rubber, injection molded poly(vinyl chloride) or leather. A new process has now been found that produces a smooth dull surface and also is non-delaminating.
- the present invention relates to a process for dulling molded block copolymer compositions comprising contacting the surface of a molded block copolymer rubber composition with an etching solution of chromic acid optionally rinsing and drying.
- a chromic acid etching solution was developed. This solution will leave small imperfections on the surface of the composition to scatter the incident light. These imperfections are too small to be seen by the naked eye but large enough to resolve light.
- the process of dulling involves contacting by for example dipping the molded article in the etching solution followed by rinsing and drying. Other methods of treatment such as brushing or spraying may be used. The mechanism of dulling may be explained as follows: When the etching solution contacts the molded article the chromic acid selectively dissolves the rubber portion of the blend producing an etched surface.
- the chromic acid etching solution may be coated or applied to the surface of the molded composition by any convenient means. These means may include dipping spraying or brushing. The solution should be applied in a uniform coat so as to obtain uniform dulling. The concentration of the solution may be varied so as to optimize for a particular method.
- the time required to achieve the desired dull look may vary depending on the concentration of the etching solution and its temperature. For example a molded article immersed in the chromic acid etching solution needed approximately 6 hours to obtain a smooth dull look.
- the dulling process may be accellerated by increasing the temperature of the etching solution. For example a dull look was obtained on a molded article in contact with the etching solution for 5 minutes at a temperature of 185° C.
- Molded articles should be rinsed with, for example, water and dryed to prevent contamination with the acid. Drying can be accomplished by any convenient means, e.g., air drying with optional heat.
- An etching solution was prepared by mixing stoichiometric amounts of chromium trioxide and concentrated sulfuric acid.
- the etching solution as above was applied to a molded styrene-butadiene-styrene block copolymer shoe sole by dipping the shoe sole in the etching solution. After rinsing and air drying, the shoe sole had a smooth, dull finish without visible surface imperfections.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention relates to a process for dulling molded block copolymer compositions comprising contacting the surface of a molded block copolymer rubber composition with an etching solution of chromic acid optionally rinsing and drying.
Description
The use of certain block copolymers and their compounds in a number of end-uses and especially in footwear, is rapidly expanding. For example, in the footwear industry, certain block copolymer compounds are being used in large volume in the manufacture of a wide variety of shoes including canvas shoes, sport shoes, and dress shoes. The block copolymers may be utilized for this purpose for soling, foxing, innersoles and the like. These compositions are disclosed in Hendricks et al, U.S. Pat. No. Re. 28,236. In general, these shoe component compositions usually comprise a mixture of block copolymer, extending oil, polystyrene and possibly a filler. For the most part, these block copolymer compositions have proven to be particularly advantageous in many respects, including flexibility, processability, lack of vulcanization requirement and wet slip. However, in certain respects, shortcomings have been noted. For example, commercial compounds should be free from delamination, free from elephant hide, and free from flow markings and marring. With respect to many styles in the casual and dress shoe areas of footwear, one of the major shortcomings of the block copolymer compounds such as those referred to in U.S. Pat. No. Re. 28,236 is the lack of a smooth appearance. Present block copolymer compounds lack the smooth, relatively unblemished surface which is characteristic of compression molded vulcanized conventional rubber, injection molded poly(vinyl chloride) or leather. A new process has now been found that produces a smooth dull surface and also is non-delaminating.
The present invention relates to a process for dulling molded block copolymer compositions comprising contacting the surface of a molded block copolymer rubber composition with an etching solution of chromic acid optionally rinsing and drying.
In order to dull the shiny surface of articles made of molded block copolymer rubber compositions a chromic acid etching solution was developed. This solution will leave small imperfections on the surface of the composition to scatter the incident light. These imperfections are too small to be seen by the naked eye but large enough to resolve light. The process of dulling involves contacting by for example dipping the molded article in the etching solution followed by rinsing and drying. Other methods of treatment such as brushing or spraying may be used. The mechanism of dulling may be explained as follows: When the etching solution contacts the molded article the chromic acid selectively dissolves the rubber portion of the blend producing an etched surface. It is believed that during etching, the unsaturated rubber phase near the surface is attacked more readily than the polystyrene phase, leading to a cavitated surface. This cavitated surface scatters the incident light causing dullness. In addition to dulling the surface of block copolymer compositions, the above process may be used to eliminate the unsightly splashes or frostings on the surface of molded articles. Presently, the industry is using a "cleaning solution" based on methyl ethylketone. This solution is relatively expensive and far inferior to the present etching solution.
The chromic acid etching solution may be coated or applied to the surface of the molded composition by any convenient means. These means may include dipping spraying or brushing. The solution should be applied in a uniform coat so as to obtain uniform dulling. The concentration of the solution may be varied so as to optimize for a particular method.
The time required to achieve the desired dull look may vary depending on the concentration of the etching solution and its temperature. For example a molded article immersed in the chromic acid etching solution needed approximately 6 hours to obtain a smooth dull look.
The dulling process may be accellerated by increasing the temperature of the etching solution. For example a dull look was obtained on a molded article in contact with the etching solution for 5 minutes at a temperature of 185° C.
Molded articles should be rinsed with, for example, water and dryed to prevent contamination with the acid. Drying can be accomplished by any convenient means, e.g., air drying with optional heat.
An etching solution was prepared by mixing stoichiometric amounts of chromium trioxide and concentrated sulfuric acid. The etching solution as above was applied to a molded styrene-butadiene-styrene block copolymer shoe sole by dipping the shoe sole in the etching solution. After rinsing and air drying, the shoe sole had a smooth, dull finish without visible surface imperfections.
Claims (6)
1. A process for dulling molded block copolymer compositions comprising contacting the surface of a molded block copolymer rubber composition with a chromic acid etching solution, optionally rinsing and drying.
2. The process of claim 1 wherein the molded composition is a styrene-butadiene block copolymer composition.
3. The process of claim 1 wherein the etching solution is sprayed on the molded composition.
4. The process of claim 1 wherein the molded composition is dipped in the etching solution.
5. The process of claim 1 wherein the etching solution is brushed on the molded composition.
6. The process of claim 1 wherein the etching solution is formed by mixing chromium trioxide and sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/603,057 US4482428A (en) | 1984-04-23 | 1984-04-23 | Smooth-look footwear process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/603,057 US4482428A (en) | 1984-04-23 | 1984-04-23 | Smooth-look footwear process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4482428A true US4482428A (en) | 1984-11-13 |
Family
ID=24413920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/603,057 Expired - Fee Related US4482428A (en) | 1984-04-23 | 1984-04-23 | Smooth-look footwear process |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US4482428A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US28236A (en) * | 1860-05-08 | Charles h | ||
| US3597336A (en) * | 1968-04-22 | 1971-08-03 | Phillips Petroleum Co | Electroplating plastics |
| US3689303A (en) * | 1970-12-21 | 1972-09-05 | Crown City Plating Co | Process for electroless plating of abs resins |
-
1984
- 1984-04-23 US US06/603,057 patent/US4482428A/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US28236A (en) * | 1860-05-08 | Charles h | ||
| US3597336A (en) * | 1968-04-22 | 1971-08-03 | Phillips Petroleum Co | Electroplating plastics |
| US3689303A (en) * | 1970-12-21 | 1972-09-05 | Crown City Plating Co | Process for electroless plating of abs resins |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: SHELL OIL COMPANY, A DE CORP. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:KARIM, KARL A.;REEL/FRAME:004297/0750 Effective date: 19840418 |
|
| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| FPAY | Fee payment |
Year of fee payment: 8 |
|
| REMI | Maintenance fee reminder mailed | ||
| LAPS | Lapse for failure to pay maintenance fees | ||
| FP | Lapsed due to failure to pay maintenance fee |
Effective date: 19961113 |
|
| STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |